Coatings, Volume 6, Issue 1 (March 2016) – 13 articles

In this paper the influence of material composition on the structural, surface and optical properties of HfO₂-TiO₂ mixed oxide coatings was investigated and discussed. Five sets of thin films were deposited using reactive magnetron sputtering: HfO₂, TiO₂ and three sets of mixed HfO₂-TiO₂ coatings with various titanium content. The change in the material composition had a significant influence on the structural, surface and optical properties. All of the deposited coatings, except for (Hf_0.55Ti_0.45)O_x, were nanocrystalline with crystallites ranging from 6.7 nm to 10.8 nm in size. Scanning electron microscopy measurements revealed that surface of nanocrystalline thin films consisted of grains with different shapes and sizes. Based on optical transmission measurements, it was shown that thin films with higher titanium content were characterized by a higher cut-off wavelength, refractive index and lower optical band gap energy. The porosity and packing density were also determined. Full article

Corrosion degradation of materials and metallic structures is one of the major issues that give rise to depreciation of assets, causing great financial outlays in their recovery and or prevention. Therefore, the development of active corrosion protection systems for metallic substrates is an issue of prime importance. The promising properties and wide application range of hybrid sol-gel-derived polymers have attracted significant attention over recent decades. The combination of organic polymers and inorganic materials in a single phase provides exceptional possibilities to tailor electrical, optical, anticorrosive, and mechanical properties for diverse applications. This unlimited design concept has led to the development of hybrid coatings for several applications, such as transparent plastics, glasses, and metals to prevent these substrates from permeation, mechanical abrasion, and corrosion, or even for decorative functions. Nevertheless, the development of new hybrid products requires a basic understanding of the fundamental chemistry, as well as of the parameters that influence the processing techniques, which will briefly be discussed. Additionally, this review will also summarize and discuss the most promising sol-gel coatings for corrosion protection of steel, aluminium, and their alloys conducted at an academic level. Full article

We describe an optical coating design suitable for broad bandwidth high reflection (BBHR) at 45° angle of incidence (AOI), P polarization (Ppol) of femtosecond (fs) laser pulses whose wavelengths range from 800 to 1000 nm. Our design process is guided by quarter-wave HR coating properties. The design must afford low group delay dispersion (GDD) for reflected light over the broad, 200 nm bandwidth in order to minimize temporal broadening of the fs pulses due to dispersive alteration of relative phases between their frequency components. The design should also be favorable to high laser-induced damage threshold (LIDT). We base the coating on TiO₂/SiO₂ layer pairs produced by means of e-beam evaporation with ion-assisted deposition, and use OptiLayer Thin Film Software to explore designs starting with TiO₂/SiO₂ layers having thicknesses in a reverse chirped arrangement. This approach led to a design with R > 99% from 800 to 1000 nm and GDD < 20 fs² from 843 to 949 nm (45° AOI, Ppol). The design’s GDD behaves in a smooth way, suitable for GDD compensation techniques, and its electric field intensities show promise for high LIDTs. Reflectivity and GDD measurements for the initial test coating indicate good performance of the BBHR design. Subsequent coating runs with improved process calibration produced two coatings whose HR bands satisfactorily meet the design goals. For the sake of completeness, we summarize our previously reported transmission spectra and LIDT test results with 800 ps, 8 ps and 675 fs pulses for these two coatings, and present a table of the LIDT results we have for all of our TiO₂/SiO₂ BBHR coatings, showing the trends with test laser pulse duration from the ns to sub-ps regimes. Full article

This paper reviews the current state of the art related to the synthesis and characterization of hybrid organic-inorganic (O/I) coatings obtained through the exploitation of dual-cure processes, which involve a photo-induced polymerization followed by a thermal treatment: this latter allows the occurrence of sol-gel reactions of suitable alkoxy precursors already embedded in the UV-curable system. After a brief introduction on hybrid organic-inorganic coatings, the first part of the review is focused on the design and feasibility issues provided by the dual-cure method, emphasizing the possibility of tuning the structure of the final hybrid network on the basis of the composition of the starting liquid mixture. Then, some recent examples of hybrid organic-inorganic networks are thoroughly described, showing their potential advances and the application fields to which they can be addressed. Full article

Bioengineering of dermal and epidermal cells on surface modified substrates is an active area of research. The cytotoxicity, maintenance of cell phenotype and long-term functionality of human dermal fibroblast (HDF) cells on conducting indium tin oxide (ITO) and semi-conducting, silicon (Si) and gallium arsenide (GaAs), surfaces modified with self-assembled monolayers (SAMs) containing amino (–NH₂) and methyl (–CH₃) end groups have been investigated. Contact angle measurements and infrared spectroscopic studies show that the monolayers are conformal and preserve their functional end groups. Morphological analyses indicate that HDFs grow well on all substrates except GaAs, exhibiting their normal spindle-shaped morphology and exhibit no visible signs of stress or cytoplasmic vacuolation. Cell viability analyses indicate little cell death after one week in culture on all substrates except GaAs, where cells died within 6 h. Cells on all surfaces proliferate except on GaAs and GaAs-ODT. Cell growth is observed to be greater on SAM modified ITO and Si-substrates. Preservation of cellular phenotype assessed through type I collagen immunostaining and positive staining of HDF cells were observed on all modified surfaces except that on GaAs. These results suggest that conducting and semi-conducting SAM-modified surfaces support HDF growth and functionality and represent a promising area of bioengineering research. Full article

Sol-gel methodologies are advantageous in the preparation of hybrid materials in front of the conventional addition of nanoparticles, because of the fine dispersion of the inorganic phase that can be reached in epoxy matrices. In addition, the use of organoalkoxysilanes as coupling agents allows covalent linkage between organic and inorganic phases, which is the key point in the improvement of mechanical properties. The sol-gel process involves hydrolysis and condensation reactions under mild conditions, starting from hydrolysable metal alkoxides, generally alkoxy silanes. Using the sol-gel procedure, the viscosity of the formulation is maintained, which is an important issue in coating applications, whereas the transparency of the polymer matrix is also maintained. However, only the proper combination of the chemistries and functionalities of both organic and inorganic structures leads to thermosets with the desired characteristics. The adequate preparation of hybrid epoxy thermosets enables their improvement in characteristics such as mechanical properties (modulus, hardness, scratch resistance), thermal and flame resistance, corrosion and antimicrobial protection, and even optical performance among others. Full article

Surface modification of dental implants is a key process in the production of these medical devices, and especially titanium implants used in the dental practice are commonly subjected to surface modification processes before their clinical use. A wide range of treatments, such as sand blasting, acid etching, plasma etching, plasma spray deposition, sputtering deposition and cathodic arc deposition, have been studied over the years in order to improve the performance of dental implants. Improving or accelerating the osseointegration process is usually the main goal of these surface processes, but the improvement of biocompatibility and the prevention of bacterial adhesion are also of considerable importance. In this review, we report on the research of the recent years in the field of surface treatments and coatings deposition for the improvement of dental implants performance, with a main focus on the osseointegration acceleration, the reduction of bacterial adhesion and the improvement of biocompatibility. Full article

In the present research the antimicrobial activity of two active packaging materials on the spoilage microbiota of fresh salmon fillets was tested. A PET-coated film (PET: Polyethylene Terephthalate) containing lysozyme and lactoferrin was tested in parallel with a carvacrol-coextruded multilayer film. Salmon fillet samples were stored up to four days at 0 and 5 °C, comparatively. The carvacrol multilayer film was found effective in preventing mesophiles and psychrotrophs at shorter storage time and at lower temperature (4.0 compared to 5.0 log CFU/g in the control sample—CFU: Colony Forming Units). Lysozyme/lactoferrin-coated PET was instead efficient in decreasing H₂S-producing bacteria at longer storage time and higher temperature (2.7 instead of 4.7 log CFU/g in the control sample). Even if is not intended as a way to “clean” a contaminated food product, an active package solution can indeed contribute to reducing the microbial population in food items, thus lowering the risk of food-related diseases. Full article

This study was aimed at developing new films based on isotactic polypropylene (iPP) for food packaging applications using zinc oxide (ZnO) with submicron dimension particles obtained by spray pyrolysis. To improve compatibility with iPP, the ZnO particles were coated with stearic acid (ZnOc). Composites based on iPP with 2 wt % and 5 wt % of ZnOc were prepared in a twin-screw extruder and then filmed by a calender. The effect of ZnOc on the properties of iPP were assessed and compared with those obtained in previous study on iPP/ZnO and iPP/iPPgMA/ZnO. For all composites, a homogeneous distribution and dispersion of ZnOc was obtained indicating that the coating with stearic acid of the ZnO particles reduces the surface polarity mismatch between iPP and ZnO. The iPP/ZnOc composite films have relevant antibacterial properties with respect to E. coli, higher thermal stability and improved mechanical and impact properties than the pure polymer and the composites iPP/ZnO and iPP/iPPgMA/ZnO. This study demonstrated that iPP/ZnOc films are suitable materials for potential application in the active packaging field. Full article

The design of anti-icing surfaces presents an interface with high causal density that has been challenging to quantify in terms of individual contributions of various interactions and environmental factors. In this commentary, we highlight the role of interfacial water structure as uniquely expressing the physico-chemical aspects of ice accretion. Recent work on the topic that focuses on control of interfacial structure is discussed along with results by our research group on wettability of chemically modified surfaces and the role of ions in modulating interfacial structure. Suggestions for systematic studies to understand the fundamental interactions at play in ice adhesion at interfaces are made especially in the under-explored areas of cooperative hydrogen bonding and the role of solvated counterions. Insights expected from such studies would contribute to design of robust anti-icing hierarchies. Full article

Titanium nitride (TiN) not only was utilized in the wear-resistant coatings industry but it was also adopted in barrier processes for semiconductor manufacturing. Barrier processes include the titanium (Ti) and TiN processes, which are commonly used as diffusion barriers in via/contact applications. However, engineers frequently struggle at the via/contact module in the beginning of every technology node. As devices shrink, barrier processes become more challenging to overcome the both the physical fill-in and electrical performance requirements of advanced small via/contact plugs. The aim of this paper is to investigate various chemical vapor deposition (CVD) TiCl₄-based barrier processes to serve the application of advanced small via/contact plugs and the metal gate processes. The results demonstrate that the plasma-enhanced chemical vapor deposition (PECVD) TiCl₄-based Ti process needs to select a feasible process temperature to avoid Si surface corrosion by high-temperature chloride flow. Conventional high step coverage (HSC) CVD TiCl₄-based TiN processes give much better impurity performance than metal organic chemical vapor deposition (MOCVD) TiN. However, the higher chloride content in HSC film may degrade the long-term reliability of the device. Furthermore, it is evidenced that a sequential flow deposition (SFD) CVD TiCl₄-based process with multiple cycles can give much less chloride content, resulting in faster erase speeds and lower erase levels than that of conventional HSC TiN. Full article

There is increasing research towards the substitution of petrochemicals by sustainable components. Biopolymers such as proteins, polysaccharides, and lipids derive from a variety of crop sources and most promisingly from waste streams generated during their processing by the agro food industry. Among those, proteins of different types such as whey, casein, gelatin, wheat gluten, soy protein or zein present a potential beyond the food and feed industry for the application in packaging. The general protein hydrophilicity promotes a good compatibility to polar surfaces, such as paper, and a good barrier to apolar gases, such as oxygen and carbon dioxide. The present review deals with the development of protein-based coatings and films. It includes relevant discussion for application in paper or board products, as well as an outlook on its future industrial potential. Proteins with suitable functionalities as food packaging materials are described as well as the different technologies for processing the coatings and the current state of the art about the coating formulations for selectively modulating barrier, mechanical, surface and end of life properties. Some insights onto regulations about packaging use, end of life and perspectives of such natural coating for decreasing the environmental impact of packages are given. Full article